JPH02258655A - Heat-radiation reflecting laminated plate - Google Patents

Abstract

PURPOSE:To improve the strength, safety, transmittance of visible light and reflectance of heat-radiation by preparing the 1st transparent plate and the 2nd transparent plate each having a specific heat-radiation reflecting film on the inner side face and laminating the transparent plates with a transparent resin film. CONSTITUTION:A pair of bus bars 11, 12 are extended on a pair of oppositely placed upper and lower sides 10a, 10b of the inner side faces of the 1st transparent plate 10. Heat-radiation reflecting films 15 are formed on the bus bars 11, 12. The heat-radiation reflecting film 16 is composed of an electrically conductive 1st metal oxide layer 16 composed of an Sn=-doped In2O3, SnO2 or ZnO and having a specific resistance of 1X10<-4>-1X10<-2>OMEGA.cm and a thickness of 100-600Angstrom , a noble metal layer 17 having a thickness of 30-300Angstrom and a 2nd metal oxide layer 18 composed of SnO2, In2O3, Sn-doped In2O3, ZnO, Bi2O3, TiO2 or Sb2O3 and having a thickness of 100-800Angstrom . Almost whole surface of the 1st transparent plate 10 is laminated to the 2nd transparent plate 19 having nearly the same shape using a transparent resin film 20.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a laminated board in which a pair of transparent plates made of glass, synthetic resin, etc. are laminated with an intermediate film made of transparent synthetic resin, that is, a transparent resin film. This laminated board has heat ray reflective performance. This heat ray reflective laminated plate is suitable for use as a vehicle window glass (particularly an automobile windshield or rear glass) or a building window glass.

[Summary of the invention]

The present invention provides a bonded temporary structure in which first and second transparent plates are laminated with a transparent resin film, and a heat ray reflective film coated on the inner surface of the first transparent plate,
It consists of first and second metal oxide layers and a noble metal layer with a thickness of 30 Å to 300 nm interposed between the first and second metal oxide layers, and the first metal oxide layer is , a conductive material with a specific resistance of 1×10-4 Ω·cII and a thickness of 100 Å to 600 μm, and is made of tin-doped indium oxide (hereinafter referred to as rI TOJ).
, tin oxide, or zinc oxide, and the second metal oxide layer has a thickness of 100 Å to 800 Å and contains tin oxide, indium oxide, To, zinc oxide, bismuth oxide, titanium oxide, or antimony oxide. Further, by providing a pair of busbars electrically connected to the heat ray reflective film, 1) the heat ray reflective film has high strength, and when broken, fragments do not fly off, resulting in high safety;
Another object of the present invention is to provide a heat-reflective laminated plate that has excellent heat-reflection performance and can be easily and reliably heated with electricity by supplying power through a pair of busbars.

[Conventional technology]

BACKGROUND OF THE INVENTION Conventionally, laminated glass has been known in which a pair of glass plates made of float glass or the like are bonded together with an interlayer film, ie, a transparent resin film, made of a transparent synthetic resin such as polyvinyl butyral. This type of laminated glass has a multi-layered structure consisting of a pair of glass plates and a transparent resin film that bonds the pair of glass plates together, so it has great strength and even if the glass plate breaks, the glass will not break. The pieces of the board are stuck to the transparent resin film, so they won't fly away.
For this reason, it is highly safe.

However, when such laminated glass is used as vehicle or architectural window glass, a large amount of solar radiant energy propagates inside the vehicle or building, especially in midsummer. temperature rises excessively. Moreover, on the contrary, especially in the middle of winter, the heat inside the vehicle or building escapes to the outside, causing the temperature inside the vehicle or building to drop excessively.

Heat-reflective glass for preventing such drawbacks and maintaining a predetermined temperature inside a vehicle or a building has also been known. This heat-reflective glass is made by coating a glass plate with a heat-reflecting film, and this heat-reflecting film is made by sandwiching a thin silver layer between a pair of dielectric layers each made of a metal oxide. It is constructed by sandwiching it in an inch shape.

Such heat ray reflective glass not only has excellent heat ray reflective performance but also excellent electrical conductivity due to the presence of the silver layer. Therefore, when this heat-reflecting glass is used as a windshield for a car, the above heat-reflecting performance can prevent the temperature inside the car from rising excessively in the summer, and it can prevent the temperature inside the car from rising excessively in the winter. By applying electricity to the silver layer to heat the heat ray reflective glass using its conductivity, it is possible to remove and prevent fogging caused by ice or water droplets adhering to the glass surface.

[Problem to be solved by the invention]

However, when heating the heat ray reflective glass by applying electricity to the heat ray reflective film of the heat ray reflective glass as described above,
The pair of dielectric layers that sandwich the thin silver layer are not conductive, so even if there is a slight defect in the thin silver layer, the current flowing through the heat ray reflective film will become uneven, causing the glass plate to Abnormal localized fever.

On the other hand, when the above-mentioned heat-ray reflective glass is used as a windshield of a car, another glass plate is laminated with a transparent resin film such as polyvinyl butyral on the heat-ray reflective film side of the heat-ray reflective glass. It is preferable to use safety laminated glass. However, in this case, if the glass plate locally generates abnormal heat as described above, the transparent resin film may be scorched, so that the transparency of the laminated glass is significantly reduced in the scorched portion.

[Means to solve the problem]

The present invention has been invented to solve the above-mentioned problems, and includes a composite plate in which first and second transparent plates made of glass, synthetic resin, etc. are laminated with a transparent resin film. A heat ray reflective film is coated on the inner surface of the transparent plate so as to be interposed between the first transparent plate and the transparent resin film, and the heat ray reflective film is coated with a first metal oxide. layer, a noble metal layer, and a second metal oxide layer are sequentially formed on the inner surface of the first transparent plate;
The metal oxide layer has a specific resistance of I x 10-'Ω・(J
~I x 10-” ohm (preferably 1
・a1~1×10-3Ω・cIl) with a thickness of 100 Å~
600 Å (preferably 250 Å to 500 Å) conductive, the noble metal layer is made of either ITO, tin oxide or zinc oxide, and the noble metal layer has a thickness of 30 Å to 500 Å.
A to 300 (preferably 60 Å to 180), and the second oxide layer has a thickness of 100 Å to 800 Å.
person (preferably 300 Å to 600 people), is made of any one of tin oxide, indium oxide, ITO1 zinc oxide, bismuth oxide, titanium oxide, and antimony oxide, and furthermore, the heat ray reflective film is energized. The present invention relates to a heat ray reflective laminated plate characterized in that a pair of busbars electrically connected to the heat ray reflective film are provided to achieve this.

In the present invention, the specific resistance of the first metal oxide layer is set to 1. X
The reason why the thickness is set to 10"'Ω・CIII~lXl0-"Ω" cm and the thickness is set to 100Å~600Ω is as follows. That is, power is supplied to the heat ray reflective laminated plate according to the present invention via a pair of busbars. In this case, a highly conductive noble metal layer (
If the thickness is between 30 Å and 300 Å, its sheet resistance is typically between 2 Ω/mm and 15 Ω/mm), even if there are local defects in the first layer electrically connected to the noble metal layer. If the metal oxide layer has the resistivity and thickness as described above, current will effectively flow through the first metal oxide layer at the defective portion, so that no local abnormality will occur in the defective portion. No fever occurs. Note that if the thickness of the first metal oxide layer is less than 100 people, it will not be possible to effectively prevent abnormal heat generation locally in the defective area, and if the thickness of the first metal oxide layer is less than 600 people, If the size is too large, the reflected color tone of the resulting laminated board will become noticeable, which is undesirable in any case.

In the present invention, a protective layer made of a metal selected from titanium, zinc, tin, and tantalum or an oxide thereof is provided separately from the noble metal layer on one side or both sides of the noble metal layer. It's okay. In this case, the noble metal layer does not contact the first and/or second metal oxide layer directly but through the protective layer, so that one or both of the noble metal layers Oxidation of the side surfaces can be effectively prevented. The thickness of the protective layer is preferably 5 Å to 50 Å, and 5 Å to 50 Å.
If it is smaller than a human, it will not function well as a protective layer,
Furthermore, if the number of people is more than 50, it will be difficult to maintain the visible light transmittance of the laminated glass at 70% or more. Also,
Even if the protective layer is formed as a metal layer, it may oxidize and change into a metal oxide layer, but as long as it functions as a protective layer, it can remain a metal layer or change into a metal oxide layer. There is no difference whatsoever.

In the invention, a third metal oxide layer and a second metal oxide layer are provided between the noble metal layer (hereinafter referred to as "first noble metal layer") and the second metal oxide layer. and a second noble metal layer interposed between the third metal oxide layer, and the third metal oxide layer has a specific resistance of lXl0- 'Ω-Ql ~lXl0
-”Ω・cm (preferably, (I×1・Q, 74Ω・1
~1 × tO−'Ω・mouth) and the thickness is 100 Å to 600 people (
Preferably, the conductivity is 250 Å to 500 Å,
The second noble metal layer is made of either ITO, tin oxide or zinc oxide, and has a thickness of 30 Å to 30 Å.
0 people (preferably 60 Å to 180 people). Thereby, the heat ray reflective performance of the heat ray reflective laminated glass according to the present invention and, in some cases, the current heating performance can be further improved. In this case, the first metal oxide layer, the initial layer, and the third metal oxide layer may have the same composition, resistivity, and thickness, or may be partially or completely different from each other. It's okay to stay. In addition, when a plurality of third metal oxide layers exist, these third metal oxide layers may have the same composition, resistivity, and thickness, or some or all of these third metal oxide layers may have the same composition, resistivity, and thickness. All may be different from each other. Furthermore, the first noble metal layer and the second noble metal layer may have the same composition and thickness, and
Either or both of these may be different from each other.

In addition, when a plurality of the second noble metal layers are present, these second noble metal layers may have the same composition and thickness, or one or both of these may be different from each other.

In the present invention, the first and second transparent plates are preferably glass plates made of float glass or the like, and may be colored as necessary as long as they have the necessary visible light transmittance. Moreover, the thickness of the first and second transparent plates is
It can be selected arbitrarily depending on the purpose, but - in terms of boat fishing, 0
．． It may be 5 to 5+ct (preferably 1 to 3 ml).

In the present invention, as described above, the first metal oxide layer comprises 1. TO1 is composed of either tin oxide or zinc oxide, and the second metal oxide layer is composed of tin oxide, indium oxide, ITO1 zinc oxide, bismuth oxide, titanium oxide, or antimony oxide. Ru. In this case, the first metal oxide layer and the second metal oxide layer may be the same type of oxide,
They may be different types of oxides. In addition, the above-mentioned ITO is added to indium oxide by 3 to 20% (preferably,
5-10%) of tin. In addition, the tin oxide is usually tin oxide (SnO□
), as indium oxide, indium oxide (In20.), as zinc oxide, zinc oxide (ZnO) in a narrow sense, and as bismuth oxide, bismuth trioxide (BizOs), and , titanium dioxide (TiO□) is used as the titanium oxide, and diantimony pentoxide (SbiOs) is used as the antimony oxide.

In the present invention, the noble metal layer may be made of one or more of gold, silver, copper, palladium, and rhodium. In particular, silver has the least absorption of light in the visible range among these noble metals, so from this point of view, it is preferable that the noble metal is made of silver. However, since silver alone does not necessarily have good chemical resistance such as moisture resistance, alkali resistance, acid resistance, etc., in some cases, the above-mentioned noble metals may contain silver as a main component,
Further, it is more preferable that the material contains a small amount of at least one of gold, copper, palladium, and rhodium. In this case, by incorporating these precious metals into silver,
The color tone of the noble metal layer may change compared to when silver is used alone, and the visible light transmittance may decrease. Therefore, the above content is preferably 2% or less for each of gold and copper, and for palladium and rhodium,
Each content is preferably 1% or less. Furthermore, even when a plurality of these types are contained, it is preferable that the total content is 2% or less.

In the present invention, the transparent resin film has substantially the same refractive index as the first and second transparent plates (for example, about 1.52 in the case of a glass plate), and and has good adhesion to the heat ray reflective film, and
The material is not particularly limited as long as it is transparent in the visible range. As the transparent resin film, for example, polyvinyl alcohol resin such as polyvinyl butyral, vinyl acetate resin such as ethylene vinyl acetate,
A film made of either thermoplastic polyurethane resin or polyvinyl chloride resin can be used, and it is particularly preferred to use a film made of polyvinyl butyral. In addition, its thickness is 0.05 to 0.4 w
(preferably 0.1 to 0.2 mm).

The heat ray reflective laminated board according to the present invention can generally be manufactured as follows.

That is, first, by performing screen printing and baking, a pair of bus bars each having a power feeding point are formed on the inner surface of the first glass plate. In this case, these pair of bus bars are formed so as to extend along a pair of mutually opposing sides of the first glass plate. Next, a first metal oxide layer, a noble metal layer, and a second metal oxide layer are sequentially formed on the inner surface of the first glass plate.

Then, after sequentially laminating this first glass plate, sheet-shaped transparent resin film, and second glass plate, this laminated body is
By heating to 30 to 180°C and applying pressure of +r/- to 1 to 5, the transparent resin film is coated on the second metal oxide layer of the first glass plate and the inner surface of the second glass plate. Heat-seal each. This laminate is then cut and sized around its periphery.

When the heat ray reflective laminated board according to the present invention is used as a window glass for a vehicle or a building, the above-described laminated board is usually placed so that the first transparent plate coated with the heat ray reflective film is on the outside of the vehicle or building. Heat reflective laminates can be attached to vehicles or buildings.

〔Example〕

Next, embodiments of the present invention will be described based on the attached drawings.

First, the heat ray reflective laminated plate according to the first embodiment of the present invention will be explained based on FIGS. 1 and 2. On the inner surface of the first glass plate 10, a pair of Side 1
A pair of bus bars 11 and 12 are provided to extend along 0a and 10b, respectively. and,
These busbars 11.12 are provided with extensions 11a and 12a that extend to the vicinity of side 10b, respectively, and the tip portions of these extensions 11a and 12b extend to the vicinity of side 10b.
A power supply terminal, that is, a power supply point 13, 14 is configured near the.

These busbars 11.12 are on busbar 1L12.
A heat ray reflective film 15 is provided so as to span between the two. Note that, as shown in FIG. 1, the heat ray reflecting film 15 can be formed on the first glass plate IO except for the outer periphery, if necessary. The heat ray reflective film 15 also includes a first metal oxide layer 16, a noble metal layer 17. and a second metal oxide layer 18 are sequentially formed on the inner surface of the first glass plate 10.

A second glass plate 19 having substantially the same shape as the first glass plate 10 is arranged opposite to the inner surface of the first glass plate 10 provided with a pair of bus bars 11, 12 and a heat ray reflective film 15, respectively. ing. These first and second glass plates 10.19 are bonded together over almost the entire surface thereof with a transparent resin film 20.

Therefore, a power supply (not shown) is connected to the pair of power supply terminals 13 and 14.
For example, a voltage of several tens of volts boosted from a 12V storage battery is transferred to the pair of power supply terminals 13.
14, the heat ray reflective film 15 has a vertical direction (
Current flows in the vertical direction (in Fig. 1). For this purpose, the outer surface of the first glass plate 10 of the heat ray reflective laminated plate is heated to, for example, several degrees Celsius to about 10 degrees Celsius.

Next, a heat ray reflective laminated plate according to a second embodiment of the present invention will be explained based on FIG. 3. This heat ray reflective laminated plate has the following characteristics: It has substantially the same structure as the heat ray reflective laminated plate shown in FIG. 1 and FIG. 2, and therefore, the common parts are given the same reference numerals and the explanation thereof will be omitted.

In FIG. 3, a pair of bus bars 1112 extend along a pair of left and right opposing sides 10c and lOd of the first glass plate 10, respectively. Therefore, if 1# voltage is applied to the pair of power supply terminals 13 and 14 in the same manner as in the first embodiment shown in FIGS. 1 and 2, the heat ray reflective film 1
5, a current flows in its lateral direction (left-right direction in FIG. 3).

FIG. 4 shows a sputtering apparatus used for manufacturing the heat ray reflective laminated plates shown in FIGS. 1 to 3.

In FIG. 4, the sputtering apparatus has a vacuum chamber 22 which is grounded by an earth line 21, and an exhaust port 24 provided with a variable valve 23 is formed in a part of the vacuum chamber 22. The vacuum chamber 22 is connected to this exhaust port 2.
4 to a vacuum pump (not shown), and the pressure inside the vacuum chamber 22 is reduced by this vacuum pump.

At the bottom of the vacuum chamber 22, magnetron cathodes 27.28 are provided spaced apart from each other via electrical insulators 25.26, and these cathodes 27.28 are connected to an on/off switch 29.30 and a DC power source 31. .32 are connected to each other. In addition, each magnetron cathode 27.2
In the vicinity of 8, supply pipes 31, 32 are provided which extend through the bottom of the vacuum chamber 22. Furthermore, supply ports 33.34 are provided at the tips of these supply pipes 31.32, and valves 35.36 are provided in the supply pipes 31.32 outside the vacuum chamber 22. There is. Oxygen gas is supplied into the vacuum chamber 22 from the gas supply pipe 31, and inert gas such as argon gas is supplied into the vacuum chamber 22 from the gas supply pipe 32.

A reciprocating conveyor 40 is arranged in the vacuum chamber 22 above the cathodes 27,28. The transport conveyor 40 includes a pair of pulleys 41 and 42 provided near both left and right ends of the vacuum chamber 22, and a conveyor belt 43 that extends over each of these pulleys 41 and 42.

Next, a method for manufacturing the heat ray reflective laminated board shown in FIGS. 1 and 2 using the suba-tuttering apparatus shown in FIG. 4 will be described.

First, an ITO target 45 is placed on the top surface of the cathode 27.
Furthermore, Ag targets 46 were attached to the upper surfaces of the cathodes 28, respectively.

Next, for example, the first glass plate 1 is provided with a pair of bus bars 11.12 having a width of 29 mm and a thickness of 20 μm.
0 was held in a holder 44 with the busbars 11 and 12 facing downward as shown in FIG. and,
This holder 44 was placed on the conveyor belt 43.

In this case, the first glass plate 10 has a bronze-colored thickness of 2.5 mm. Itm was used. In order to form the pair of bus bars 11 and 12 in advance, a mixture consisting of fine silver particles, an organic resin binder, and a low-melting glass lift is applied by screen printing, and the glass plate is bent (at a temperature of 580 to 600°C). ) at the same time. Moreover, on the inner surface of the first glass plate 10,
If the masking material is applied in advance in a shape along the outer periphery, the first and second metal oxide layers 16, 18 and the noble metal layer 17 are formed on the outer periphery. It never happens.

Next, the variable valve 23 was opened to once reduce the pressure in the vacuum chamber 22 to a high vacuum. Then, by opening the valve 35, a mixed gas of argon gas and oxygen gas is supplied from the supply port 33 of the gas supply pipe 31, and the inside of the vacuum chamber 22 is equilibrated to 1.5 x 10 Torr. Ta. The mixing ratio of this mixed gas is, for example, argon gas 100 m I
The ratio of oxygen gas to t/min was 5 mj'/mi.

Next, by turning on the on/off switch 29, a negative voltage was applied to the cathode 27 to cause a current to flow, and this current caused sputtering.

Also, around this time, the conveyor belt 43 was
By moving the conveyor belt 43 in the left and right direction from one side to the other at a speed of m/min.
The upper glass plate 10 was moved in the same manner. As a result, as shown in FIG. 2, the surface of the glass plate 10 has a specific resistance of 8.
An ITO film, ie, the first metal oxide layer 16, was formed with a thickness of 360 mm and a value of OX 10-'Ω. This ITO film 16 consisted of 10% tin oxide and 90% indium oxide.

Next, switch 29 is turned off, valve 35 is closed, variable valve 23 is opened, and vacuum chamber 22 is closed.
The inside was once reduced to a high vacuum.

Then, by opening the valve 36, argon gas is supplied from the supply port 34 of the gas supply pipe 32 to 100 m I
1.4X inside the vacuum chamber 22 by supplying l/+++in.
Equilibrated to 10-'' Torr.

Next, by turning on the on/off switch 30, a negative voltage was applied to the cathode 28 to cause a current to flow, causing sputtering.

Also, around this time, the conveyor belt 43 was
By moving the conveyor belt 43 in the left and right direction from one side to the other at a speed of m/min.
The upper glass plate 10 was moved in the same manner. As a result, on the surface of the first metal oxide 1i16 of the glass plate 10, as shown in FIG. 2, an Ag film having a thickness of 150 mm, that is, a noble metal layer 17 was formed.

Next, turn off the on/off switch 30, set the valve 36 to the closed position, and open the variable valve 23.
The pressure inside the vacuum chamber 22 was once reduced to a high vacuum. Then, by opening the valve 35, argon gas (100 mjl/min) is supplied from the supply port 33 of the gas supply pipe 31.
The inside of the vacuum chamber 22 is heated to 1.5
Equilibrated to .

Next, by turning on the on/off switch 29, a negative voltage was applied to the cathode 27 to cause a current to flow, and this current caused sputtering.

Also, around this time, the conveyor belt 43 was
By moving the conveyor belt 43 in the left and right direction from one side to the other at a speed of m/min.
The upper glass plate 10 was moved in the same manner. As a result, as shown in FIG. 2, the surface of the noble metal layer 17 of the glass plate 10 has a specific resistance of 8. An ITO film, ie, the second metal oxide layer 18, was formed with a thickness of 540 μm and a value of OX 10−′Ω·.

Next, the first metal oxide layer 16, the noble metal layer 17 and the second
A first glass plate l on which metal oxide layers 18 of
O was taken out from the vacuum chamber 22 of the sputtering apparatus shown in FIG. Then, the masking material previously applied to the first glass plate 10 was removed using a solvent.

Next, on the second metal oxide layer 18 of the bronze-colored glass plate 0, a transparent resin film 2° consisting of a polyvinyl butyral film with a thickness of 0.15n+ and a 2° thick film are applied.
1 fl transparent glass plates 19 were sequentially laminated. Then, after heating this laminate to 150'lll:,
g/an! The polyvinyl butyral film 19 was thermally fused to the second metal oxide layer 18 of the glass plate 10 and to the inner surface of the glass plate 19 by applying pressure at a pressure of .

Next, the periphery of this laminate was cut to size it to a desired size, and as a result, a heat ray reflective laminated plate as shown in FIGS. 1 and 2 was obtained.

Next, in the embodiments described above, the first metal oxide layer 16
The thickness of the first metal oxide layer 16 may be changed from 360 to 420, or the first metal oxide layer 16 may be changed from ITO to ZnO, or the thickness made of Ti may be A first protective layer of 50% Ti is formed between the noble metal layer 17 and the second metal oxide layer 18.
Provide a second protective layer for the person or the second metal oxide 118
Heat ray reflective laminated plates were produced in the same manner by changing the thickness from 540 to 420 and by changing the second metal oxide layer 18 from ITO to ZnO.

The following Table 1 shows the structure of each layer of the heat ray reflective film 15 of the examples of the present invention (samples 1 to 4) and the comparative example (comparative sample) of the heat ray reflective laminated plates obtained as described above. It is shown. In addition, the following Table 2 shows the optical properties of each sample shown in Table 1 (visible light transmittance and Hunter color tone a, b of transmitted visible light, visible light reflectance and Hunter color tone a of reflected visible light, b) is shown. (here,
"Hunter color tone a, bJ means color tone display a, b of the Hunter display system.) Among the samples in Tables 1 and 2, sample 1 is This was obtained by the above-mentioned embodiment described based on FIGS. 2 and 4.

(The following is a blank space, continued on the next page.) From Tables 1 and 2 above, examples of the present invention (Samples 1 to 2)
The heat ray reflective laminated board of 4) has higher visible light transmittance, its hunter color tone, and visible light rays than the heat ray reflective laminated board of the comparative example (comparative sample) in which the first metal oxide layer 16 is not conductive. It is clear that both the reflectance and the Hunter tone are comparable.

Next, the results of energization tests for examples of the present invention (samples 1 to 4) and comparative examples (comparative samples) will be described.

First, the object to be subjected to the energization test was created as follows. That is, in Samples 1 to 4 and the comparative sample, the transparent resin film 20 and the second glass plate 19 were not yet laminated, and these samples (i.e., the bus bar 11.1
2 and a first glass plate 10 on which a heat ray reflective film 15 is formed.
), as shown in FIG.
I added it only in a few places. This scratch 51 is, as shown in FIG.
The tip 52a of the ballpoint pen 52 is brought into contact with the heat ray reflective film 15 at an angle of 60@, and in this contact state, the angle of 50
It was formed by inflicting a length of 30** at a speed of m/win. At this time, the downward loads in the axial direction of the ballpoint pen 52 are 500 g, 750 g,
There were four types: 1,000g and 1,500g.

The width of the scratch 51 is approximately 0 at the minimum load (500g).
．． 2 cranes, approximately 0.4 at maximum load (1,500g)
It was 11 to 0.5 mm.

Next, the second glass plate 19 was attached to the first glass plate 10 with the transparent resin film 20 in between, as described above. Then, a voltage was applied to the heat ray reflective film 15 for 10 minutes via the pair of bus bars 11 and 12, and a current of 1.0 OOW/m was caused to flow. In this case, if abnormal heating occurs locally in the heat ray reflective film 15, the transparent resin film 19 will be scorched by the heat, and the refractive index of the heat ray reflective laminated plate will locally change at this scorched portion. Therefore, by transmitting light through the heat ray reflective laminated plate, it was examined whether or not the above-mentioned change in refractive index occurred.

Table 3 below shows the results of this test.

Table 3 From Table 3 above, it is clear that in the case of the example of the present invention, no locally abnormal heating occurred, but in the case of the comparative example, locally abnormal heating occurred. It is.

Note that even in the case of the comparative example, abnormal heating occurs locally in the case of elongated scratches 51 extending parallel to the bus bars 11 and 12, but circular scratches and scratches extending almost perpendicular to the bus bars 11 and 12 cause abnormal heating locally. It was found that abnormal local heating rarely occurs in the case of

〔Effect of the invention〕

As described above, the present invention has a multilayer structure in which a first transparent plate having a heat ray reflective film coated on its inner surface and a second transparent plate are laminated with a transparent resin film, so that the strength is increased. is large and difficult to break.

In addition, since the first transparent plate and the second transparent plate are bonded together with a transparent resin film, even if they break, the pieces of the first and second transparent plates will stick to the transparent resin film. Because I have
The fragments will not fly away, so safety is high.

Further, the laminate coated as a heat ray reflective film on the inner surface of the first transparent plate includes a first metal oxide layer having a thickness of 100 Å to 600 Å and made of ITO1 tin oxide or zinc oxide; A noble metal layer with a thickness of 30 Å to 300 Å and a second metal oxide layer of 100 Å to 800 Å thick made of tin oxide, indium oxide, rTO1 zinc oxide, bismuth oxide, titanium oxide, or antimony oxide, It is constructed by sequentially forming them on the inner surface of a transparent plate. Therefore, since the laminate functions as a good optical interference film, it has high visible light transmittance and excellent heat ray reflection performance.

Further, a pair of bus bars electrically connected to the heat ray reflection film are provided to supply electricity to the heat ray reflection film. Therefore, it is possible to very easily supply power to the heat ray reflective film through these pair of busbars, so that heating by energization is very easy.

In addition, the heat ray reflective film has a specific resistance of 1 x 10-4 Ω・c, apart from the noble metal layer that has high conductivity but is not very thick.
m~I
0 conductive first metal oxide layer. Therefore, when power is supplied to the heat ray reflective film, the current flows to the extent that it not only affects the noble metal layer but also the first metal oxide layer, so even if there is a defect such as a scratch on the noble metal layer, the defect is not locally heated abnormally.

[Brief explanation of drawings]

FIG. 1 is a plan view of a heat ray reflective laminated plate according to a first embodiment of the present invention in which the transparent resin film and the second glass plate are omitted, and FIG. FIG. 3 is a sectional view taken along the line I-1 in FIG. 1 with the plate not omitted, and FIG. 3 is a plan view similar to FIG. 1 of the heat ray reflective laminated plate according to the second embodiment of the present invention. , FIG. 4 is a schematic vertical cross-sectional view of a sputtering apparatus used for manufacturing heat ray reflective laminated plates according to the first and second embodiments of the present invention, and FIG. Figure 6 is a diagram similar to Figure 1 to explain the energization test conducted on
FIG. 3 is a longitudinal cross-sectional view of a main part of a heat ray reflective film being damaged with a ballpoint pen for explaining the energization test same as above. In addition, in the symbols used in the drawings, 1a----1...-1111, first glass plate 11.12--...-Bus bar 15--... −・・・−・−・・Heat ray reflective film 16
−・−・・・−・−・・−First metal oxide layer 17
−・−・−・−−−−−−・−Precious metal layer 18・・−・−
・−・−・−・・Second metal oxide layer 19−・
・・−・−・−・−・・−・・・Second glass plate 2
0-・・−・−・−・−・− It is a transparent resin film.

Claims (1)

[Scope of Claims] 1. A laminated board in which a first transparent plate and a second transparent plate are laminated together with a transparent resin film, wherein the first transparent plate and the second transparent plate are attached to the inner surface of the first transparent plate. A heat ray reflective film is deposited to be interposed between the transparent resin film, and the heat ray reflective film covers the first metal oxide layer, the noble metal layer, and the second metal oxide layer. The first metal oxide layer has a specific resistance of 1×10^-^4.
Ω・cm ~ 1×10^-^2 Ω・cm and thickness is 100Å
The noble metal layer has a thickness of 30 Å to 300 Å and is conductive with a thickness of 30 Å to 300 Å, and is composed of one of (1) tin-doped indium oxide, (2) tin oxide, and (3) zinc oxide. Yes, the second metal oxide layer has a thickness of 100 Å to 800 Å
consisting of any one of (i) tin oxide, (ii) indium oxide, (iii) tin-doped indium oxide, (iv) zinc oxide, (v) bismuth oxide, (vi) titanium oxide, (vi) and antimony oxide. and furthermore, a heat ray reflective laminated board characterized in that a pair of bus bars electrically connected to the heat ray reflective film are provided to supply electricity to the heat ray reflective film. 2. The pair of bus bars are interposed between the first transparent plate and the first metal oxide layer and extend along a pair of opposing sides of the heat ray reflective film, respectively. 2. The heat ray reflective laminated plate according to claim 1, wherein the heat ray reflective laminated plate is attached to an inner surface of the first transparent plate. 3. The heat ray reflective laminated board according to claim 1 or 2, wherein each of the pair of bus bars is provided with a power feeding point. 4. A protective layer made of one of titanium, zinc, tin, and tantalum or an oxide thereof is provided on both sides of the noble metal layer, respectively. Heat ray reflective laminate as described. 5. between the noble metal layer and the second metal oxide layer,
at least one set consisting of a third metal oxide layer and a second noble metal layer interposed between the second metal oxide layer and the third metal oxide layer; The third metal oxide layer has a specific resistance of 1×10^-^4
Ω・cm ~ 1×10^-^2 Ω・cm and thickness is 100Å
The second noble metal layer has a conductivity of ~600 Å and is composed of any one of (1) tin-doped indium oxide, (2) tin oxide, and (3) zinc oxide, and the second noble metal layer has a thickness of 30 Å. The heat ray reflective laminated board according to any one of claims 1 to 4, characterized in that the thickness is 300 Å. 6. Any one of claims 1 to 5, wherein the first and second transparent plates are each glass plates.
The heat ray reflective laminate described in . 7. The heat ray reflection according to any one of claims 1 to 6, wherein the noble metal layer is made of one or more of gold, silver, copper, palladium, and rhodium. Sex matching board. 8. According to any one of claims 1 to 7, the noble metal layer is mainly composed of silver and contains a small amount of at least one of gold, copper, palladium, and rhodium. heat ray reflective laminate. 9. The heat ray reflective laminated board according to any one of claims 1 to 7, wherein the noble metal layer is made of silver. 10. The heat ray reflective laminated board according to any one of claims 1 to 9, wherein the transparent resin film is made of polyvinyl butyral.